This invention relates to compositions containing a special enzyme system for coloring keratin fibers, to their use and to corresponding processes for coloring keratin fibers.
By virtue of their intensive colors and good fastness properties, so-called oxidation colorants play a prominent role in the coloring of keratin fibers, particularly human hair. Oxidation colorants contain oxidation dye precursors, so-called primary intermediates and secondary intermediates. The primary intermediates form the actual dyes with one another or by coupling with one or more secondary intermediates in the presence of oxidizing agents or atmospheric oxygen.
In general, natural-looking hair colors cannot be obtained solely with a primary intermediate or with a special primary intermediate/secondary intermediate combination. In practice, therefore, combinations of various primary intermediates and/or secondary intermediates are normally used.
The primary intermediates normally used are primary aromatic amines containing another free or substituted hydroxy or amino group in the para or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and derivatives thereof.
Special representatives are, for example, p-phenylenediamine, p-toluylenediamine, 2,4,5,6-tetraaminopyrimidine, p-aminophenol, N,N-bis-(2-hydroxyethyl)-p-phenylenediamine, 2-(2,5-diaminophenyl)-ethanol, 2-(2,5-diaminophenoxy)-ethanol, 1-phenyl-3-carboxyamido4-amino-5-pyrazolone, 4-amino-3-methylphenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 1,3-N,Nxe2x80x2-bis-(2xe2x80x2-hydroxyethyl)-N,Nxe2x80x2-bis-(4xe2x80x2-aminophenyl)-diamino-2-propanol.
The secondary intermediates used are generally m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols. Particularly suitable secondary intermediates are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-5-pyrazolone, 2,4-dichloro-3-aminophenol, 1,3-bis-(2,4-diaminophenoxy)-propane, 2-chlororesorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenoll, 2-methyl resorcinol, 5-methyl resorcinol and 2-methyl-4-chloro-5-aminophenol.
In principle, the color can be oxidatively developed with atmospheric oxygen. However, a chemical oxidizing agent is preferably used. Suitable oxidizing agents are persulfates, chlorites and, above all, hydrogen peroxide or addition products thereof with urea, melamine and sodium borate. A 2-9% aqueous hydrogen peroxide solution is normally used. The keratin fibers can be damaged by such high concentrations of oxidizing agent, particularly where they have already been xe2x80x9cpermedxe2x80x9d or bleached. In some cases, skin irritation can also be caused by these high concentrations.
A significant start to solving this problem is to reduce the concentration of oxidizing agent. Accordingly, attempts have already been made on the one hand to find dye precursors which, by virtue of their chemical structure, can be oxidized even by relatively small quantities of hydrogen peroxide or by atmospheric oxygen. On the other hand, it has been proposed to use enzymes as biocatalysts which are capable of catalyzing the desired oxidation process with very little, if any, hydrogen peroxide simply in the presence of atmospheric oxygen.
DE-OS 2 155 390 describes an enzyme-activated oxidative hair coloring process in which small quantities of H2O2 are used in combination with a peroxidase enzyme. EP-A1-0 310 675 also discloses enzymatic hair treatment preparations which contain at least one dielectron-reducing oxidase that uses oxygen as acceptor. EP-B1 0 548 620 describes enzymatic hair colorants where oxidation of the dye precursors is catalyzed by the use of a peroxidase. Finally, EP-A2 0 795 313 describes enzymatic hair colorants which contain an oxygen-oxidoreductase/substrate system and a peroxidase and, as a compulsory secondary intermediate, an m-phenylenediamine derivative. However, none of these colorants has yet proved totally convincing in terms of their coloring performance (intensity, tone, brilliance, fastness properties).
Readily oxidizable dye precursors have the disadvantage, along with the enzymatic color development hitherto described, that the results they give in regard to intensity, brilliance and color fastness properties are poorer by comparison with the conventional processes.
Accordingly, the problem addressed by the present invention was to provide colorants for keratin fibers which would enable the fibers to be treated without damage and at the same time would guarantee excellent coloring performance.
It has now surprisingly been found that high-performance colorants with distinct advantages in terms of fiber and skin care are obtained if they contain at least one dye precursor, a choline-based oxidase system and at least one peroxidase.
Keratin fibers in the context of the invention are understood to be pelts, wool, feathers and in particular human hair.
According to the invention, a choline-based oxidase system is understood to be choline oxidase in combination with choline as substrate. Choline is oxidized by choline oxidase in accordance with the following reaction scheme: 
For the purposes of the present invention, choline is preferably used in the form of a salt with a physiologically compatible organic or inorganic acid. Examples of such salts are the chloride, the bromide, the iodide, the citrate, the hydrogen tartrate, the hydrogen carbonate, the methyl sulfate and the p-toluenesulfonate. Choline chloride is particularly preferred.
Choline oxidase (EC 1.1.3.17) can be obtained from various sources. One occurrence was found, for example, in human cells. Choline oxidase produced by Alcaligenes species and Arthrobacter globiformis is particularly preferred for the purposes of the invention. Choline oxidases are commercially available and are marketed, for example, by Sigma. According to the invention, the activity of the choline oxidase is defined as follows: one unit [1 U] of choline oxidase catalyzes the oxidation of 1 xcexcmol of choline to betaine aldehyde in one minute at pH 8.0/37xc2x0 C., 1 xcexcmol of H2O2 being formed (according to Sigma""s definition of the commercial products).
Choline oxidase is used in the compositions according to the invention in quantities of 1 to 50,000 U per 100 g of coloring preparation. Quantities of 1 to 10,000 U per 100 g of coloring preparation are preferred, the range from 400 to 5,000 U per 100 g of coloring preparation being most particularly preferred.
According to the invention, the substrate choline is used in quantities of 1 to 5% by weight, based on the coloring preparation as a whole.
Besides the choline-based oxidase system, the compositions according to the invention also contain a peroxidase (EC 1.11.1.7). The peroxidases may be obtained from animals, plants or fungi. Vegetable peroxidases and fungus-based peroxidase can be particularly preferred for the purposes of the invention, soybean peroxidase being most particularly preferred.
In another embodiment of the present invention, peroxidases with a minimal catalase content, for example horse radish peroxidase, are preferably used.
According to the invention, the activity of the peroxidase is defined as follows: 1 unit [1 U] of peroxidase forms 1.0 mg of purpurogallin from pyrogallol in 20 seconds at pH 6.0/20xc2x0 C. (according to Sigma""s definition of the commercial products).
According to the invention, the peroxidase is used in a quantity of 1 to 100,000 U. Quantities of 1 to 10,000 U are preferred, a quantity of 1 to 500 U being most particularly preferred. The quantities mentioned are all based on 100 g of coloring preparation.
The compositions according to the invention are distinguished by their hair- and skin-preserving effect. Hair treated in accordance with the invention has greater smoothness, higher tensile strength and lower porosity than hair colored by conventional coloring techniques.
In a first embodiment of the present invention, the dye precursor may be an oxidation dye precursor of the primary intermediate type. However, several primary intermediates may also be used in the compositions according to the invention.
According to the invention, preferred primary intermediates are p-phenylenediamine, p-toluylenediamine, p-aminophenol, o-aminophenol, 1-(2xe2x80x2-hydroxyethyl)-2,5-diaminobenzene, N,N-bis-(2-hydroxyethyl)-p-phenylenediamine, 2-(2,5-diaminophenoxy)-ethanol, 1-phenyl-3-carboxyamido-4-amino-5-pyrazolone, 4-amino-3-methylphenol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2-hydroxyethylaminomethyl-4-aminophenol, 4,4xe2x80x2-diaminodiphenylamine, 4-amino-3-fluorophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, bis-(2-hydroxy-5-aminophenyl)-methane, 1,4-bis-(4-aminophenyl)-diazacycloheptane, 1,3-bis-(N-(2-hydroxyethyl)-N-(4-aminophenylamino))-2-propanol, 1,8-bis-(2,5-diaminophenoxy)-3,6-dioxaoctane, 4-amino-2-(2-hydroxyethoxy)-phenol and 4,5-diaminopyrazole derivatives according to EP 0 740 931 or WO 94/08970, for example 4,5-diamino-1-(2xe2x80x2-hydroxyethyl)-pyrazole.
Particularly preferred primary intermediates are p-phenylenediamine, p-toluylenediamine, p-aminophenol, 1-(2xe2x80x2-hydroxyethyl)-2,5-diaminobenzene, 4-amino-3-methylphenol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 4,5-diamino-1-(2-hydroxyethyl)-pyrazole, 2-aminomethyl-4-aminophenol, N,N-bis-(2-hydroxyethyl)-p-phenylenediamine, 1,8-bis-(2,5-diaminophenoxy)-3,6-dioxaoctane, bis-(2-hydroxy-5-aminophenyl)-methane and o-aminophenol.
Most particularly preferred primary intermediates are 1-methyl-2,5-diaminobenzene, 4-amino-2-aminomethylphenol, p-aminophenol, 4-hydroxy-2,5,6-triaminopyrimidine, 1-(2xe2x80x2-hydroxyethyl)-2,5-diaminobenzene and N,N-bis-(2-hydroxyethyl)-1,4-diaminobenzene.
The compositions according to the invention may additionally contain one or more secondary intermediates for shading the color tones obtained. According to the invention, preferred secondary intermediates are 1-naphthol, pyrogallol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, o-aminophenol, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-5-pyrazolone, 2,4-dichloro-3-aminophenol, 1,3-bis-(2,4-diaminophenoxy)-propane, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methyl resorcinol, 5-methyl resorcinol, 2,5-dimethyl resorcinol, 2,6-dihydroxypyridine, 2,6-diaminopyridine, 2-amino-3-hydroxypyridine, 2,6-dimethoxy-3,5-diaminopyridine, 2,6-dihydroxy-3,4-diaminopyridine, 3-amino-2-methylamino-6-methoxypyridine, 4-amino-2-hydroxytoluene, 2,6-bis-(2-hydroxyethylamino)-toluene, 2,4-diaminophenoxyethanol, 1-methoxy-2-amino-4-(2-hydroxyethylamino)-benzene, 2-methyl-4-chloro-5-aminophenol, 6-methyl-1,2,3,4-tetrahydroquinoxaline, 3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline, 2,6-dimethyl-3-aminophenol, 3-amino-6-methoxy-2-methylaminophenol, 2-hydroxy-4-aminophenoxy ethanol, 2-methyl-5-(2-hydroxyethylamino)-phenol and 2,6-dihydroxy-3,4-dimethyl pyridine.
Particularly preferred secondary intermediates for the purposes of the invention are 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, resorcinol, 1,3-bis-(2,4-diaminophenoxy)-propane, 2,4-dichloro-3-aminophenol, 4-chlororesorcinol, 2-amino-3-hydroxypyridine, 2,6-dimethoxy-3,5-diaminopyridine, 2-chloro-6-methyl-3-aminophenol, 2-methyl-4-chloro-5-aminophenol, 2-methyl resorcinol, 5-methyl resorcinol, 2,5-dimethyl resorcinol, 2,6-bis-(2-hydroxyethylamino)-toluene, 2,6-dihydroxy-3,4-diaminopyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,4-diaminophenoxy ethanol, 1-methoxy-2-amino-4-(2-hydroxyethylamino)-benzene, 6-methyl-1,2,3,4-tetrahydroquinoxaline, 3,4-methylenedioxy aniline, m-aminophenol, o-aminophenol and 2-chlororesorcinol.
Most particularly preferred secondary intermediates are 2,4-diaminophenoxy ethanol, 2-chloro-6-methyl-3-aminophenol, 5-amino-2-methylpenol, 1,3-bis-(2,4-diaminophenoxy)-propane, 2-methyl resorcinol and 1-methoxy-2-amino-4-(2-hydroxyethylamino)-benzene.
The primary and secondary intermediates are normally used in free form. However, compounds containing amino groups may preferably be used in salt form, more particularly in the form of the hydrochlorides and sulfates.
The following primary intermediate/secondary intermediate combinations have proved to be particularly suitable for the purposes of the invention:
4-aminophenol/5-amino-2-methylphenol
1-methyl-2,5-diaminobenzene/2,4-diaminophenoxyethanol
4-amino-2-aminomethylphenol/2-chloro-6-methyl-3-aminophenol
4-amino-2-aminomethylphenol/2,4-diaminophenoxy ethanol
1-methyl-2,5-diaminobenzene/5-amino-2-methylphenol
1-methyl-2,5-diaminobenzene/1,3-bis-(2,4-diaminophenoxy)-propane
4-hydroxy-2,5,6-triaminopyridine/2-methylresorcinol
1-(xcex2-hydroxyethyl)-2,5-diaminobenzene/2,4-diaminophenoxy ethanol
N,N-bis-(xcex2-hydroxyethyl)-1,4-diaminobenzene/1-methoxy-2-amino-4-(2-hydroxyethylamino)-benzene.
The hair colorants according to the invention contain both the primary intermediates and the secondary intermediates in a quantity of preferably 0.005 to 20% by weight and more preferably 0.1 to 5% by weight, based on the oxidation colorant as a whole. The primary intermediates and secondary intermediates are generally used in a substantially equimolar ratio to one another. Although it has proved to be of advantage to use the primary and secondary intermediates in an equimolar ratio, there is no disadvantage in using individual oxidation dye precursors in a certain excess so that primary intermediates and secondary intermediates may be present in a molar ratio of 1:0.5 to 1:3 and more particularly 1:1 to 1:2.
In a second embodiment of the present invention, the dye precursor may be a derivative of indoline. Preferred examples are derivatives of 5,6-dihydroxyindoline corresponding to formula (Ia): 
in whichxe2x80x94independently of one another xe2x80x94R1 is hydrogen, a C1-4 alkyl group or a C1-4 hydroxyalkyl group, R2 is hydrogen or a xe2x80x94COOH group, the xe2x80x94COOH group optionally being present as a salt with a physiologically compatible cation, R3 is hydrogen or a C1-4 alkyl group, R4 is hydrogen, a C1-4 alkyl group or a group xe2x80x94COxe2x80x94R6, where R6 is a C1-4 alkyl group, and R5 is one of the groups mentioned for R4,
or a physiologically compatible salt of these compounds with an organic or inorganic acid.
In a third embodiment of the present invention, the dye precursor may be a derivative of indole. Preferred examples are derivatives of 5,6-dihydroxyindole corresponding to formula (Ib): 
in whichxe2x80x94independently of one another xe2x80x94R1xe2x80x2 is hydrogen, a C1-4 alkyl group or a C1-4 hydroxyalkyl group, R2xe2x80x2 is hydrogen or a xe2x80x94COOH group, the xe2x80x94COOH group optionally being present as a salt with a physiologically compatible cation, R3xe2x80x2 is hydrogen or a C1-4 alkyl group, R4xe2x80x2 is hydrogen, a C1-4 alkyl group or a group xe2x80x94COxe2x80x94R6xe2x80x2, where R6xe2x80x2 is a C1-4 alkyl group, and R5xe2x80x2 is one of the groups mentioned for R4xe2x80x2,
or a physiologically compatible salt of these compounds with an organic or inorganic acid.
Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid, 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline. Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.
5,6-Dihydroxyindoline and 5,6-dihydroxyindole are most particularly preferred.
In a first variant of the embodiments described above, the compositions are formulated in such a way that they only contain indole and/or indoline derivatives as oxidation dye precursors and are free from typical oxidation dye precursors of the primary intermediate/secondary intermediate type.
In a second variant of the embodiments described above, the compositions according to the invention also contain typical oxidation dye precursors of the primary intermediate/secondary intermediate type in addition to the indole and/or indoline derivatives. In this variant, the indoline or indole derivative may preferably be used in combination with one or more secondary intermediates in hair colorants. Attention is specifically drawn at this juncture to the secondary intermediates mentioned above as preferred.
In another preferred embodiment of the invention, the indoline or indole derivative may be used in combination with at least one amino acid or one oligopeptide in hair colorants. The amino acid is advantageously an xcex1-amino acid; most particularly preferred xcex1-amino acids are arginine, ornithine, lysine and histidine.
In another preferred embodiment, the hair colorants according to the invention may contain typical substantive dyes in addition to the dye precursors to further modify the shades. Substantive dyes are normally nitrophenylendiamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are the compounds known under the International names or trade names of HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, HC Blue 12, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17 and also 4-amino-2-nitrodiphenylamine-2xe2x80x2-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, hydroxyethyl-2-nitrotoluidine, picramic acid, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.
The colorants according to the invention of this embodiment contain the substantive dyes in a quantity of preferably 0.01 to 20% by weight, based on the colorant as a whole.
The compositions according to the invention may also contain naturally occurring dyes such as, for example, henna red, henna neutral, henna black, camomile blossom, sandalwood, black tea, black alder bark, sage, logwood, madder root, catechu, sedre and alkanet.
The dye precursors or the substantive dyes do not have to be single compounds. On the contrary, other components may be present in small quantities in the hair colorants according to the invention due to the processes used to produce the individual dyes providing these other components do not adversely affect the coloring result or have to be ruled out for other reasons, for example toxicological reasons.
So far as the dyes suitable for use in the hair colorants and tinting compositions according to the invention are concerned, reference is also expressly made to the work by Ch. Zviak, The Science of Hair Care, Chapter 7 (pages 248-250; substantive dyes) and Chapter 8, pages 264-267; oxidation dye precursors), published as Volume 7 of the Series xe2x80x9cDermatologyxe2x80x9d (Ed.: Ch. Culnan and H. Maibach), Marcel Dekker Inc., New York/Basel, 1986, and to the xe2x80x9cEuropxc3xa4ische Inventar der Kosmetik-Rohstoffexe2x80x9d published by the Europxc3xa4ische Gemeinschaft and available in disk form from the Bundesverband Deutscher Industrie- und Handelsunternehmen fxc3xcr Arzneimittel, Reformwaren und Kxc3x6rperpflegemittel d.V., Mannheim.
Hair colorants based on the choline oxidase system with a pH of 7 to 10 and more particularly 8 to 9 are preferred. It has been found in accordance with the invention that particularly intensive and brilliant colors are obtained if the composition has a pH value of about 8.3. The pH value of the hair colorant is preferably adjusted with a tris-(hydroxymethyl)-aminomethane/potassium chloride buffer system.
Besides the choline oxidase system according to the invention, the colorants according to the invention may contain other oxidases with their respective substrates. Examples are glucose oxidase, alcohol oxidase, pyruvate oxidase, oxalate oxidase, cholesterol oxidase, uricase, lactate oxidase, xanthine oxidase, pyranose oxidase, glycerol oxidase and galactose oxidase. Compositions which contain glucose oxidase and/or xanthine oxidase and their respective substrates in addition to the choline oxidase system are preferred.
To produce the colorants according to the invention, the dye precursors may be incorporated in a suitable water-containing carrier. For coloring hair, such carriers are, for example, creams, emulsions, gels or even surfactant-containing foaming solutions, for example shampoos, foam aerosols or other formulations suitable for application to the hair.
The colorants according to the invention may also contain any of the known active substances, additives and auxiliaries typical of such formulations. In many cases, the colorants contain at least one surfactant, both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants being suitable in principle. If necessary, the expert may check the various surfactants for any effects on the activity of the enzyme system according to the invention by carrying out simple preliminary tests.
In one preferred embodiment of the present invention, a combination of anionic and nonionic surfactants or a combination of anionic and amphoteric surfactants is used in the compositions for coloring keratin fibers.
However, it has proved to be of advantage in individual cases to select the surfactants from amphoteric or nonionic surfactants because they generally have less influence on the coloring process according to the invention.
Suitable anionic surfactants for the hair colorants according to the invention are any anionic surface-active substances suitable for use on the human body. Such substances are characterized by a water-solubilizing anionic group such as, for example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group containing around 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may also be present in the molecule. The following are examples of suitable anionic surfactantsxe2x80x94in the form of the sodium, potassium and ammonium salts and the mono-, di- and trialkanolammonium salts containing 2 or 3 carbon atoms in the alkanol group:
linear fatty acids containing 10 to 22 carbon atoms (soaps),
ether carboxylic acids corresponding to the formula Rxe2x80x94Oxe2x80x94(CH2xe2x80x94CH2O)xxe2x80x94CH2xe2x80x94COOH, in which R is a linear alkyl group containing 10 to 22 carbon atoms and x=0 or 1 to 16,
acyl sarcosides containing 10 to 18 carbon atoms in the acyl group,
acyl taurides containing 10 to 18 carbon atoms in the acyl group,
acyl isethionates containing 10 to 18 carbon atoms in the acyl group,
sulfosuccinic acid mono- and dialkyl esters containing 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters containing 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups,
linear alkane sulfonates containing 12 to 18 carbon atoms,
linear xcex1-olefin sulfonates containing 12 to 18 carbon atoms,
xcex1-sulfofatty acid methyl esters of fatty acids containing 12 to 18 carbon atoms,
alkyl sulfates and alkyl polyglycol ether sulfates corresponding to the formula Rxe2x80x94O(CH2xe2x80x94CH2O)xxe2x80x94SO3H, in which R is a preferably linear alkyl group containing 10 to 18 carbon atoms and x=0 or 1 to 12,
mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,
sulfated hydroxyalkyl polyethylene and/or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354,
sulfonates of unsaturated fatty acids containing 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,
esters of tartaric acid and citric acid with alcohols in the form of addition products of around 2 to 15 molecules of ethylene oxide and/or propylene oxide with fatty alcohols containing 8 to 22 carbon atoms.
Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids containing 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule and, in particular, salts of saturated and, more particularly, unsaturated C8-22 carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.
Ampholytic surfactants are surface-active compounds which, in addition to a C8-18 alkyl or acyl group, contain at least one free amino group and at least one xe2x80x94COOH or xe2x80x94SO3H group in the molecule and which are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkyl aminobutyric acids, N-alkyl iminodipropionic acids, N-hydroxyethyl-N-alkyl amidopropyl glycines, N-alkyl taurines, N-alkyl sarcosines, 2-alkyl aminopropionic acids and alkyl aminoacetic acids containing around 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkyl amino-propionate, cocoacyl aminoethyl aminopropionate and C12-18 acyl sarcosine.
Nonionic surfactants contain, for example, a polyol group, a poly-alkylene glycol ether group or a combination of polyol and polyglycol ether groups as the hydrophilic group. Examples of such compounds are
products of the addition of 2 to 30 moles of ethylene oxide and/or 0 to 5 moles of propylene oxide onto linear fatty alcohols containing 8 to 22 carbon atoms, onto fatty acids containing 12 to 22 carbon atoms and onto alkylphenols containing 8 to 15 carbon atoms in the alkyl group,
C12-22 fatty acid monoesters and diesters of products of the addition of 1 to 30 moles of ethylene oxide onto glycerol,
C8-22 alkyl mono- and oligoglycosides and ethoxylated analogs thereof,
products of the addition of 5 to 60 moles of ethylene oxide onto castor oil and hydrogenated castor oil,
products of the addition of ethylene oxide onto sorbitan fatty acid esters,
products of the addition of ethylene oxide onto fatty acid alkanolamides and
amine oxides.
Alkyl polyglycosides corresponding to formula (II):
R6xe2x80x94Oxe2x80x94(Z)xxe2x80x83xe2x80x83(II)
in which R6 is an alkyl group containing 8 to 22 carbon atoms, Z is a mono- or oligosaccharide and x is a number of 1.1 to 5, are particularly preferred nonionic surfactants. These compounds are characterized by the following parameters.
The alkyl group R6 contains 8 to 22 carbon atoms and may be both linear and branched. Primary linear and 2-methyl-branched aliphatic groups are preferred. Corresponding alkyl groups are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl and 1-myristyl are particularly preferred. Where so-called xe2x80x9coxo alcoholsxe2x80x9d are used as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.
The alkyl polyglycosides usable in accordance with the invention may contain only one particular alkyl group R6. Normally, however, these compounds are produced from natural fats and oils or mineral oils. In this case, the alkyl groups R6 are mixtures corresponding to the starting compounds of to the particular working up of these compounds.
Particularly preferred alkyl polyglycosides are those in which R6 consists
essentially of C8 and C10 alkyl groups,
essentially of C12 and C14 alkyl groups,
essentially of C8 to C16 alkyl groups or
essentially of C12 to C16 alkyl groups.
Any mono- or oligosaccharides may be used as the sugar unit Z. Sugars containing 5 or 6 carbon atoms and the corresponding oligosaccharides are normally used. Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose. Preferred sugar units are glucose, fructose, galactose, arabinose and sucrose. Glucose is particularly preferred.
The alkyl polyglycosides usable in accordance with the invention contain on average 1.1 to 5 sugar units. Alkyl glycosides with x-values of 1.3 to 2 are preferred. Alkyl glycosides in which x is 1.4 to 1.6 are most particularly preferred.
Amine oxides corresponding to general formula (VI):
R7R8R9Nxe2x86x92Oxe2x80x83xe2x80x83(III)
in which R7 is a branched or unbranched C8-18 alkyl chain and R8 and R9 independently of one another represent a C1-3 alkyl group or a C1-3 hydroxyalkyl group, are also preferred.
Another amine oxide usable in accordance with the invention is the amine oxide WS 35 marketed by Tego(copyright) Cosmetics in which R8 and R9 represent methyl groups and R7 is a cocoacyl amidopropyl group.
In the context of the invention, zwitterionic surfactants are surface-active compounds which contain at least one quaternary ammonium group and at least one xe2x80x94COO(xe2x88x92) or xe2x80x94SO3(xe2x88x92) group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl-N,N-dimethyl ammonium glycinates, for example cocoalkyl dimethyl ammonium glycinate, N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for example cocoacylaminopropyl dimethyl ammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name of Cocamidopropyl Betaine.
Examples of the cationic surfactants suitable for use in the hair treatment formulations according to the invention are, in particular, quaternary ammonium compounds. Preferred quaternary ammonium compounds are ammonium halides, such as alkyl trimethyl ammonium chlorides, dialkyl dimethyl ammonium chlorides and trialkyl methyl ammonium chlorides, for example cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetyl methyl ammonium chloride. Other cationic surfactants suitable for use in accordance with the invention are the quaternized protein hydrolyzates.
Also suitable for use in accordance with the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silyl amodimethicone), Dow Corning 929 Emulsion (containing a hydroxylamino-modified silicone which is also known as Amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil(copyright)-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethyl siloxanes, Quaternium-80).
Alkyl amidoamines, particularly fatty acid amidoamines, such as the stearyl amidopropyl dimethyl amine obtainable as Tego Amid(copyright)S 18, are distinguished not only by their favorable conditioning effect, but also and in particular by their ready biodegradability.
Quaternary ester compounds, so-called xe2x80x9cesterquatsxe2x80x9d, such as the methyl hydroxyalkyl dialkoyloxyalkyl ammonium methosulfates marketed under the trade name of Stepantex(copyright) and the products marketed under the name of Dehyquart(copyright), such as Dehyquart AU-46, are also readily biodegradable.
One example of a quaternary sugar derivative suitable for use as a cationic surfactant is the commercially available product Glucquat(copyright) 100 (INCI name: Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride).
The compounds containing alkyl groups used as surfactants may be single compounds. In general, however, these compounds are produced from native vegetable or animal raw materials so that mixtures with different alkyl chain lengths dependent upon the particular raw material are obtained.
The surfactants representing addition products of ethylene and/or propylene oxide with fatty alcohols or derivatives of these addition products may be both products with a xe2x80x9cnormalxe2x80x9d homolog distribution and products with a narrow homolog distribution. Products with a xe2x80x9cnormalxe2x80x9d homolog distribution are mixtures of homologs which are obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. By contrast, narrow homolog distributions are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be of advantage.
Other active substances, auxiliaries and additives are, for example,
nonionic polymers such as, for example, vinyl pyrrolidone/vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone/vinyl acetate copolymers and polysiloxanes,
cationic polymers, such as quaternized cellulose ethers, polysiloxanes containing quaternary groups, dimethyl diallyl ammonium chloride polymers, acrylamide/dimethyl diallyl ammonium chloride copolymers, dimethyl aminoethyl methacrylate/vinyl pyrrolidone copolymers quaternized with diethyl sulfate, vinyl pyrrolidone/imidazolinium methochloride copolymers and quaternized polyvinyl alcohol,
zwitterionic and amphoteric polymers such as, for example, acrylamidopropyl/trimethyl ammonium chloride/acrylate copolymers and octyl acrylamide/methyl methacrylate/tert.butyl aminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers,
anionic polymers such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate/crotonic acid copolymers, vinyl pyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers and acrylic acid/ethyl acrylate/N-tert.butyl acrylamide terpolymers,
thickeners, such as agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, for example methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives, such as amylose, amylopectin and dextrins, clays such as, for example, bentonite or fully synthetic hydrocolloids such as, for example, polyvinyl alcohol,
structurants, such as glucose, maleic acid and lactic acid,
hair-conditioning compounds, such as phospholipids, for example soybean lecithin, egg lecithin and kephalins, and also silicone oils,
protein hydrolyzates, more particularly elastin, collagen, keratin, milk protein, soybean protein and wheat protein hydrolyzates, condensation products thereof with fatty acids and quaternized protein hydrolyzates,
perfume oils, dimethyl isosorbide and cyclodextrins,
solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,
antidandruff agents, such as Piroctone Olamine and Zinc Omadine,
other substances for adjusting the pH value,
active principles, such as panthenol, pantothenic acid, allantoin, pyrrolidone carboxylic acids and salts thereof, plant extracts and vitamins, amino acids
cholesterol,
UV filters,
consistency factors, such as sugar esters, polyol esters or polyol alkyl ethers,
fats and waxes, such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters,
fatty acid alkanolamides,
complexing agents, such as EDTA, NTA and phosphonic acids,
swelling and penetration agents, such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,
opacifiers, such as latex,
pearlizers, such as ethylene glycol mono- and distearate,
propellents, such as propane/butane mixtures, N2O, dimethyl ether, CO2 and air and
antioxidants.
To produce the colorants according to the invention, the constituents of the water-containing carrier are used in the usual quantities for this purpose. For example, emulsifiers are used in concentrations of 0.5 to 30% by weight while thickeners are used in concentrations of 0.1 to 25% by weight, based on the colorant as a whole.
The enzyme preparation is preferably mixed with the preparation of dye precursors immediately before coloring of the hair. The application temperatures may be in the range from 15 to 40xc2x0 C. After a contact time of about 5 to 30 minutes, the hair colorant is removed from the hair to be colored by rinsing. There is no need for the hair to be washed with a shampoo where a carrier of high surfactant content, for example a coloring shampoo, has been used.
To accelerate the coloring process, an aqueous solution of the oxidase system may preferably be separately adjusted to the required pH before mixing with the coloring preparation and preincubated for 30 mins. at 37xc2x0 C., for example in a shaking hood. The preincubation mixture is then incorporated in the coloring cream. Finally, the peroxidase is added.
In another embodiment of the invention, the enzyme preparation is preferably formulated without antioxidants and/or complexing agents because they can block the effect of the enzymes.